ES2825323T3 - Derivatives of maleate natural oils as agrochemical adjuvants - Google Patents

Abstract

An adjuvant composition comprising a maleate compound obtained from the reaction of (1) a maleate oil derived from renewable raw material resources that have been reacted in an ene reaction with an α, β-unsaturated carboxylic acid or anhydride that introduced additional carboxylic fractions or the related anhydrous structure in the oil molecules with (2) a compound comprising at least one polyetheramine, wherein the molar ratio of the maleate oil (1) with the compound (2) is greater than 1.1: 1.

Description

DESCRIPTION

Derivatives of maleate natural oils as agrochemical adjuvants

FIELD OF THE INVENTION

The present disclosure is directed to adjuvant compositions containing a product obtained from the reaction of a maleate natural oil and a compound comprising at least one polyetheramine and their use in agrochemical formulations.

BACKGROUND OF THE INVENTION

In addition to active ingredients, agrochemical formulations also contain inert ingredients that make agrochemical formulations easier to handle, more convenient to apply, and / or more effective. Many different classes of inert ingredients are available for use including emulsifiers, dispersants and adjuvants, and can, depending on their type, improve the wetting, spreading, adhesion, emulsifying, dispersing and / or the biological activity of the agrochemical formulation.

There is no universal inert ingredient that can improve the performance of all active ingredients. Therefore, the inert ingredient (s) selected and the relative amounts used must be adapted to the specific conditions of each application. Examples include:

US Patent No. 5,495,033, which discloses a methylated acidulated soy soap solution that can be used with various herbicides;

US Patent No. 5,521,144, which teaches a post-emergent herbicide adjuvant that includes an acidified soap solution combined with an alkylphenol ethoxylate or a mixture of an alcohol ethoxylate and glycol ether or an anionic surfactant;

US Patent No. 5,658,855, which describes the combination of an amine or ammonia compound, an ammonium salt, a nonionic surfactant having a high HLB, and water and its use with pesticides; US Patent No. 5,888,934, which discloses an inert ingredient for improving resistance to rain that includes an alkylpolyglucoside and an ethoxylated alcohol obtained from the ethoxylation of an aliphatic monoalcohol;

US Patent No. 5,928,563, which teaches an adjuvant containing a sulfated alkyl oleate, an alkylpolyglucoside, and a C6-Cis alkyl ester;

US Patent No. 5,942,542, which describes inert ingredients for use with a pyrethroid insecticide comprising an alkyl ester of a fatty acid having an unsaturation level of at least 40% or an alkyl ester of a dibasic acid and a nonionic emulsifier;

US 2003/0104947, which discloses the combination of a petroleum oil with a pH adjuster, and a non-ionic surfactant and its use in agrochemical formulations;

US Patent No. 6,642,178, which teaches an adjuvant for use in spray carriers comprising a nitrogen fertilizer, a modified vegetable oil, a pH adjuster, and a mixture of high, intermediate, and non-ionic surfactants. low HLB;

WO 2004/080177, which describes an adjuvant in the form of a microemulsion containing a hydrocarbon or fatty acid ester, an alkylpolyglucoside, a glycerol or sorbitan ester and water;

US 2005/0129662 which discloses the use of vegetable oil as an adjuvant;

US 2011/0201504, which discloses an adjuvant mixture containing an alkyl fatty acid ester, at least two nonionic surfactants selected from alkyl polyglycosides, sorbitol esters and polyglycerol esters and optionally a polyol; Y

US 2013/0210630, which exemplifies ethyl maleated soybean and linseed oil as an emulsifier for an active ingredient.

Most agrochemical formulations contain more than one inert ingredient to help supply the active ingredient to weeds, insects, fungi, etc. desired goal. Some of these inert ingredients are sourced from resources that are not renewable or have inconsistent / seasonal availability. Others are persistent in the environment and have toxic biodegradation products or other unwanted side effects. Additionally, each time a new active ingredient is introduced to the market, it requires the development of a unique formulation to bring the active ingredient to the field. Therefore, there is a need to develop new versatile inert agrochemical ingredients that are non-toxic and inspired or created from renewable resources.

SUMMARY OF THE INVENTION

The present disclosure provides an adjuvant composition according to claim 1.

In another aspect, the present disclosure provides an agrochemical formulation for application on a target substrate to cause a chemical or biological effect. The agrochemical formulation comprises (i) a pesticidally effective amount of a pesticide or a mixture of pesticides and (ii) the adjuvant composition of claim 1. The adjuvant composition is present in the agrochemical formulation at a concentration such that the pesticidal efficacy of the Agrochemical formulation is increased compared to a reference agrochemical formulation devoid of the adjuvant composition of the present disclosure but which otherwise has the same ingredients as the agrochemical formulation. Thus, the addition of such an adjuvant composition to the agrochemical formulation enables faster uptake of the active ingredients by a target substrate treated with the agrochemical formulation. This improved activity can result in the following aspects in treating a target substrate with the agrochemical formulation: a comparatively higher activity of the active ingredient at a given application rate; a comparatively lower application rate to a given activity; and a comparatively greater absorption of the active ingredient by the target substrate.

In other aspects, the present disclosure provides a concentrate composition according to claim 9 and a spray formulation according to claim 10.

In yet another aspect, the present disclosure provides a method of killing, inhibiting, or repelling a pest that includes: providing the pesticide or a mixture of pesticides in a pesticidally effective amount; providing an effective amount of the adjuvant composition of claim 1; combining the pesticide or pesticide mixture with the adjuvant composition to form an agrochemical formulation; and bring the agrochemical formulation and the pest into contact.

DETAILED DESCRIPTION OF THE INVENTION

The present disclosure provides an adjuvant composition according to claim 1 comprising a derivative of maleated natural oil. The adjuvant composition can be provided to a user after it has been premixed with a pesticide or a mixture of pesticides. Alternatively, the adjunct composition can be provided to a user on its own or in a concentrated composition or spray formulation, for example.

Surprisingly, the adjuvant composition of the present disclosure has been found to be useful in agrochemical formulations to improve the efficacy of active ingredients in agrochemical formulations. By "improved" it is to be understood that the adjuvant composition comprising the maleated natural oil derivative of the present disclosure increases the performance of the active ingredients in the agrochemical formulations (eg, a higher activity of the active ingredients for a given application rate , a lower application rate with a given effect, a better absorption of the active ingredient by the target substrate and therefore advantages for a pre-emergence or post-emergence treatment, in particular the spray treatment of target substrates) compared to Agrochemical formulations that do not contain the maleate natural oil derivatives of the present disclosure. Furthermore, the maleated natural oil derivatives of the present disclosure have a surfactant-like structure with the oily part of the molecule acting as hydrophobic and the attached derivative group acting as hydrophilic. Thus, the maleated natural oil derivative is difunctional and, in some embodiments, can be used in an adjuvant composition or agrochemical formulation that is substantially free of surfactants, which is surprising and advantageous since the number of components generally added is considerably reduced. .

As used herein, the term "adjuvant composition" is a composition that enhances the bioactivity of a pesticide and has no bioactivity of its own.

The term "substantially free" means that, when used in reference to the substantial absence of a material in a formulation, such material is present, if it is, as an incidental impurity or by-product. In other words, the material does not affect the properties of the formulation.

Furthermore, a "pesticidally effective amount" refers to the amount of a pesticide that, upon application, either reduces the presence of pests or improves the resistance of a plant to a pest.

Also, the term "target substrate" refers to the sites underlying the plant foliage that are the intended destination for the pesticide including, but not limited to, natural soil surfaces such as land, water (lakes, ponds, marshes, swamps , streams, puddles, etc.) and artificial surfaces such as pavement; a plague; or a combination thereof.

A "pest" generally includes insects, mites, ticks, and other arthropods; pathogens such as fungi, protozoa, bacteria, and viruses; helminths, nematodes (roundworms), cestodes (tapeworms), flatworms (flat worms), trematodes (trematodes) and other worms; sporozoan parasites; slugs and snails; and vertebrates such as birds, rodents or other vertebrates that can damage or cause disease or damage directly or indirectly to any plant or part thereof or any processed, manufactured or other plant product.

The term "comprising" and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not it is disclosed herein. For the avoidance of doubt, all compositions claimed herein by use of the term "comprising" may include any additional additives or compounds, unless otherwise indicated. On the contrary, the term "consisting essentially of" if it appears herein, excludes from the scope of any subsequent recitation any other component, step or procedure, except those that are not essential for operability and the term "consisting of" , if used, excludes any component, step or procedure not specifically defined or listed. The term "or", unless otherwise indicated, refers to the members listed individually as well as in any combination.

The articles "a" and "one" are used herein to refer to one or more than one (ie, at least one) of the article's grammatical object. By way of example, "a maleated natural oil derivative" means one maleated natural oil derivative or more than one maleated natural oil derivative.

The phrases "in one embodiment", "in accordance with an embodiment" and the like generally mean that the particular feature, structure, or characteristic that follows the phrase is included in at least one embodiment of the present invention, and may be included in more of an embodiment of the present invention. It is important to note that such phases do not necessarily refer to the same performance.

If the specification states that a component or feature "may", or "could" be included or have a feature, that particular component or feature is not required to be included or have the feature.

Adjuvant composition

The adjuvant composition of the present disclosure includes a maleated natural oil derivative. The maleated natural oil derivative can be obtained from the reaction of a maleated natural oil and a derivative compound comprising at least one polyetheramine.

In one embodiment, the natural oil used to prepare the maleated natural oil derivative of the present disclosure is derived from renewable raw material resources such as natural and / or genetically modified (GMO) plant seeds and / or fats of animal origin. Such vegetable seeds or fats of animal origin include oils and / or fats that are generally composed of triglycerides, that is, fatty acids linked together with glycerol. For example, the natural oil can have at least about 70 percent unsaturated fatty acids in the triglyceride, while in another embodiment, the natural oil can have at least 85 percent by weight unsaturated fatty acids. Such unsaturated fatty acids have at least one allyl hydrogen or "ene moiety" present in the fatty portion of the fatty acid.

In one embodiment, the natural oil is a vegetable oil such as, but not limited to, castor oil, soybean oil, olive oil, peanut oil, rapeseed oil, corn oil, sesame oil, cottonseed oil, canola oil, safflower oil, flaxseed oil, palm oil, grapeseed oil, black caraway oil, pumpkin oil, grain oil, borage seed oil, wood germ oil, seed oil apricot, pistachio oil, almond oil, macadamia nut oil, avocado oil, sea buckthorn oil, hemp oil, hazelnut oil, evening primrose oil, wild rose oil, thistle oil, walnut oil , sunflower oil, jatropha seed oil, or a combination thereof. In addition, natural oils obtained from organisms such as algae can also be used. Examples of natural oils of animal origin include lard, beef tallow, fish oils, and mixtures thereof. A combination of vegetable oil, oil obtained from algae and / or oils of animal origin can also be used. In one embodiment, the natural oil is not corn oil.

Natural oils, as described herein, also include fatty acids or fatty acid esters derived from natural oils or fats. That is, the term "natural oil" also includes unsaturated fatty acids and corresponding esters thereof. Examples of such unsaturated fatty acids include oleic acid, myristoleic acid, palmitoleic acid, linoleic acid, α-linolenic acid, arachidonic acid, icosapentaenoic acid, erucic acid, and docosahexaenoic acid. Examples of fatty acid esters include alkyl esters of vegetable oils, obtained by traditional transesterification techniques to produce products such as methyl soyate (methyl ester of soybean oil), methyl oleate (methyl oleic acid ester) and methyl canolate (methyl ester). canola oil).

Natural oils also include fatty acid glyceryl esters, which are synthesized by reacting glycerol with 1, 2, or 3 molar equivalents of a fatty acid or a mixture of fatty acids. These compounds can be mono, di or triglycerides of a single fatty acid or a mixture of fatty acids. Some examples are glyceryl dioleate, glyceryl triolate, glyceryl distearate, and glyceryl trilinoleate.

In yet another embodiment, the natural oils also include the fatty acids of a sugar or sugar alcohol. Such fatty acids are described in US Patent No. 3,600,186. The term sugar is used herein in its conventional sense as a generic for mono and disaccharides. The term sugar alcohol is also used in its conventional sense as a generic for the sugar reduction product where the aldehyde or ketone group has been reduced to an alcohol. These fatty acid ester compounds can be prepared by reacting a monosaccharide, disaccharide, or sugar alcohol with fatty acid.

Examples of suitable monosaccharides are those containing 4 hydroxyl groups such as xylose, arabinose and ribose; xylose derived sugar alcohol, ie xylitol, is also suitable. Erythrose monosaccharide is not suitable as it only contains 3 hydroxyl groups; however, the erythrose-derived sugar alcohol, ie, erythritol, contains 4 hydroxyl groups and is therefore suitable. Among the 5 hydroxyl-containing monosaccharides that are suitable for use herein are glucose, mannose, gelactose, fructose, and sorbose. A sugar alcohol derived from sucrose, glucose or sorbose, for example sorbitol, contains 6 hydroxyl groups and is also suitable as the alcohol fraction of the fatty acid ester compound. Examples of suitable disaccharides are maltose, lactose, and sucrose, all of which contain 8 hydroxyl groups.

grupos hidroxilo de un compuesto de azúcar o alcohol de azúcar, como los identificados anteriormente, deben sterificarse con un ácido graso que tenga de aproximadamente 8 a aproximadamente 22 átomos de carbono. Ejemplos de tales ácidos grasos son caprílico, cáprico, láurico, mirístico, miristoleico, palmítico, palmitoleico, esteárico, oleico, ricinoleico, linoleico, linolénico, eleosteárico, araquídico, behénico y erúcico. Los ácidos grasos per se o las grasas y aceites de origen natural pueden servir como fuente para el componente de ácido graso en el éster de ácido graso de azúcar o alcohol de azúcar. Por ejemplo, el aceite de colza es una buena fuente de ácido graso C22. El ácido graso C16-C18 puede ser proporcionado por sebo, aceite de soja o aceite de semilla de algodón. Los ácidos grasos de cadena más ocrta pueden ser proporcionados por aceites de coco, palmiste o babasú. El aceite de maíz, manteca, aceite de oliva, aceite de palma, aceite de cacahuete, aceite de semilla de cártamo, aceite de semilla de sésamo y aceite de semilla de girasol, son ejemplos de otros aceites naturales que pueden servir como fuente del componente de ácido graso.When preparing sugar or sugar alcohol fatty acid, at least

Hydroxyl groups of a sugar or sugar alcohol compound, such as those identified above, must be sterified with a fatty acid having from about 8 to about 22 carbon atoms. Examples of such fatty acids are caprylic, capric, lauric, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, linolenic, eleostearic, arachidic, behenic, and erucic. Fatty acids per se or naturally occurring fats and oils can serve as the source for the fatty acid component in the sugar or sugar alcohol fatty acid ester. For example, rapeseed oil is a good source of C22 fatty acid. The C16-C18 fatty acid can be provided by tallow, soybean oil, or cottonseed oil. The lowest chain fatty acids can be provided by coconut, palm kernel or babassu oils. Corn oil, shortening, olive oil, palm oil, peanut oil, safflower seed oil, sesame seed oil, and sunflower seed oil are examples of other natural oils that can serve as a source of the component. fatty acid.

Among the fatty acids, those that are preferred have from about 14 to about 18 carbon atoms, and are more preferably selected from the group consisting of myristic, palmitic, stearic, oleic, and linoleic. Therefore, natural fats and oils that have a high content of these fatty acids represent the preferred sources for the fatty acid components, for example, soybean oil, olive oil, cottonseed oil, corn oil, tallow. and lard.

Suitable sugar alcohol or sugar fatty acid esters for use in this invention can be prepared by a variety of methods well known to those skilled in the art. These methods include: transesterification with another ester such as methyl, ethyl, or glycerol, acylation with a fatty acid chloride; acylation with a fatty acid anhydride, and acylation with a fatty acid per se.

The following are examples of suitable sugar or sugar alcohol fatty acid esters containing at least 4 fatty acid ester groups suitable for use in the present disclosure: glucose tetraoleate, glucose tetra-stearate, fatty acid glucose tetraester soybean oil, tallow fatty acid mannose tetraester, olive oil fatty acid galactose tetraester, cottonseed fatty acid oil aribinose tetraester, xylose tetrainoleate, galactose pentasestearate, sorbitol tetraoleate, olive oil fatty acid sorbitol hexaester, xylitol pentapalrinate, substantially fully hydrogenated cottonseed oil xylitol tetraester, sucrose tetrastearate, sucrose pentastearate, sucrose hexaoleate, sucrose octaoleate, sucrose octaester of fatty acid substantially fully hydrogenated soybean oil, sucrose octaester of soybean oil fatty acid acahuete, olive oil fatty acid erythritol tetraoleate, erythritol tetraoleate, xylitol pentaoleate, sorbitol hexaoleate, sucrose octaoleate, soybean oil fatty acid sucrose octaester, and mixtures thereof.

The natural oil (or combination of natural oils) is reacted with an enophile or an enophile / dienophile mixture containing acid, semi-ester or anhydride functionality to form a maleate natural oil.

As used throughout the specification and claims, the terms "maleation", "maleation" and the like refer to modifications of natural oil molecules that introduce additional carboxylic moieties (or related anhydride structure) into oil molecules. natural by reacting natural oil with one or more than one α, p-unsaturated carboxylic acid or anhydride, for example maleic anhydride. The α, p-unsaturated carboxylic acid or anhydride may be a biogenically derived α, p-unsaturated carboxylic acid or anhydride. Non-limiting examples of biogenically derived α, p-unsaturated carboxylic acids or anhydrides include itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, acrylic acid, methacrylic acid, citraconic acid, citraconic anhydride, mesaconic acid, muconic acid, glutaconic acid, acid methylglutaconic, traumatic acid, and fumaric acid. Acids and anhydrides include any isomers (eg, enantiomers, diastereoisomers, and cis- / trans- isomers) and salts. In some embodiments, the α, p-unsaturated carboxylic acid and anhydride can be one of the following unsaturated acids: maleic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid, and mixtures thereof.

In a non-limiting example, maleic anhydride is reacted with a vegetable oil as shown below:

Reaction conditions are well known to those skilled in the art and can be found, for example, in US Patent Nos. 2,188,882 and 2,188,887. Thus, the reaction of the above non-limiting example, for illustration purposes only, may be performed at elevated temperatures, such as a temperature between about 150 ° C and about 300 ° C, alternatively between about 170 ° C and about 230 ° C, or alternatively between about 200 ° C and about 220 ° C. The reaction time can be between about 0.5 hours and about 10 hours. In one embodiment, the reaction time is between about 1 hour and about 5 hours, and in another embodiment, between about 2 hours and 4 hours.

During maleation, the molar ratio of natural oil: enophilic or enophilic / dienophilic mixture in some embodiments is less than or equal to 1, in other embodiments 0.3 to 1.0, even in other embodiments 0.50 to 1 .00, and in other embodiments more than 0.55 to 0.75 and even in additional embodiments from 0.60 to 0.70. The resulting excess oenophilic or oenophilic / dienophilic mixture helps to reduce the amount of unreacted natural oil thereby limiting the tendency to ooze.

In still other embodiments, the natural oil is maleated with at least 0.02 moles of enophile or enophile / dienophile mixture per mole of natural oil. In another embodiment, the natural oil is malleable with at least 0.5 moles of the enophilic or enophile / dienophile mixture per mole of natural oil, while in other embodiments, the natural oil is malleable with greater than about 1 mole of Enophilic or Enophilic / Dienophilic Mixture. per mole of natural oil. In additional embodiments, the natural oil is maleated with no more than 2.5 moles of enophile or enophile / dienophile mixture per mole of natural oil, while in other embodiments, the natural oil is maleate with no more than 2.25 moles. of enophile or mixture of enophile / dienophile per mole of natural oil, while in still other embodiments, the natural oil is malleable with no more than 2 moles of the mixture of enophile / dienophile per mole of natural oil. In one embodiment, the enophile used is maleic anhydride.

According to a particular embodiment, the maleate natural oil is a maleate alkyl ester of a fatty acid or a maleate synthetic triglyceride of a natural fatty acid.

The maleated natural oil is then reacted with a derivative compound comprising at least one polyetheramine, to form the maleated natural oil derivative.

The polyetheramine can be a mono-, di-, tri-, tetra-, or multifunctional polyetheramine. Methods for preparing polyetheramines are well known and can be found, for example, in US Patent Nos. 3,654,370, 3,832,402, 4,990,476, and 4,992,590. In general, polyetheramines can be produced by alkoxylating a mono-, di-, tri-, tetra-, or multifunctional alcohol or alkylphenol with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, to forming an alkylene oxide adduct, and then catalytically aminating the alkylene oxide adduct in the presence of hydrogen and ammonia to form the polyetheramine. In some embodiments, the polyetheramine can be initialized by an amine that is alkoxylated and then aminated.

According to one embodiment, the polyetheramine is a polyether monoamine having the formula (1) or (1a):

where R is hydrogen or methyl, and

a and b independently are integers from about 1 to about 150;

where Y is hydrogen or methyl,

Z is a Ci-C 40 alkyl group or a C 1 phenol group 40 alkyl carbon atoms and

w is an integer from about 1 to about 100.

In another embodiment, the polyetheramine is a polyether monoamine having the formula (2) or (2a):

Commercially available polyether monoamines include JEFFAMINE® M series and XTJ series amines, including, but not limited to, JEFFAMINE® M-600, M-1000, M-2005, M-2070, XTJ- 435 and XTJ-436, available from Huntsman Corporation.

In another embodiment, the polyetheramine is a polyether diamine having the formula (3), (4), or (5):

where c is an integer from about 2 to about 100;

where e is an integer from about 2 to about 40, and

d and f are independently integers from about 1 to about 10;

where g is an integer from about 2 to about 3.

Commercially available polyether diamines include JEFFAMINE® D, ED, and EDR amines, including, but not limited to, JEFFAMIn E® D-200, D-400, D-2000, D-4000, ED-600, ED amines. -900, ED-20003, EDR-148, and EDR-176, available from Huntsman Corporation.

In yet another embodiment, the hydrophilic polyetheramine is a polyether triamine having the formula (6):

where R1 is hydrogen, methyl or ethyl,

n is an integer of 0 or 1, and

h, i, and j are independently integers from about 1 to about 100.

Commercially available triamines include the JEFFAMINE® T series amines, including, but not limited to, JEFFAMINE® T-403, T-3000 and T-5000 amines, available from Huntsman Corporation.

In yet another embodiment, the hydrophilic polyetheramine is a polyether tetraamine having the formula:

where each R ² is independently hydrogen, methyl or ethyl,

R ³ is a C ¹ -C ⁵ alkyl group, and

each M is independently an integer from about 2 to about 50.

In yet another embodiment, the polyetheramine is a multifunctional polyetheramine. The multifunctional polyetheramine of the present disclosure can be a di-, tri- or tetraamine polyether, as described herein, having at least one of the hydrogens of the amine groups replaced by a hydroxyl group. For example, multifunctional polyetheramine may have the formula (8):

where each R4 and R5 are independently hydrogen or a hydroxyl group, provided that at least one of R4 is hydrogen and at least one of R5 is a hydroxyl group.

The molar ratio of maleate natural oil to compound comprising at least one polyetheramine is greater than 1.1: 1, in other embodiments 1.8 to 10: 1, and even 2.0 to 7.5: 1, while in other embodiments more than 2.5 to 5: 1 and in addition 3.0 to 3.5: 1.

The reaction of the maleate natural oil and the compound comprising at least one polyetheramine can proceed without special considerations and is known to those skilled in the art. In general, it can proceed in a temperature range between about 20 ° C and about 260 ° C and in a pressure range between about 1 and about 10 atm (0.1 to 1 MPa) in the presence or absence of antioxidants based on den common phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, polyisobutylene phenol, tocopherol (vitamin E family) and the like and mixtures thereof. Lewis acid catalysts can be used to improve the reaction rate, but catalysts are not generally used.

In some embodiments, the adjuvant composition may consist of the maleate natural oil while in other embodiments the adjuvant composition may comprise the maleate natural oil and an auxiliary component. In some embodiments, some or all of the auxiliary component (s) may instead be added during formation of the agrochemical formulation described below.

Examples of auxiliary components include, but are not limited to, solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, humectants, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants. , repellants, attractants, food stimulants, compatibilizers, bactericides, antifreeze agents, crystallization inhibitors, antifoam agents, colorants, tackifiers, binders, preservatives, inorganic or organic acids to neutralize pH, clarifiers, stabilizers, fertilizers such as fertilizers of ammonium sulfate, urea or compounds, for example compound fertilizers based on phosphorus, potassium and nitrogen, such as P, K, N fertilizers, UV stabilizers and mixtures thereof.

Liquid solvents and carriers can be water and organic solvents such as: medium to high boiling mineral oil fractions, eg kerosene, diesel oil; natural oils such as those described above and biodiesel oil; aliphatic, cyclic and aromatic hydrocarbons, eg toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, eg, ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, for example cyclohexanone; esters, for example lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, eg, N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. In one embodiment, the solvent is an organic solvent.

The crystallization inhibitors can be polyacrylic acids and their salts, although the latter are preferred. The polyacrylic acid salts can be ammonium, primary, secondary, or tertiary ammonium derivatives, or alkali metal salts (eg, sodium, potassium, lithium ions), wherein in one embodiment alkali metal salts are preferred as the salts. of sodium. Polyacrylic acids and their salts usually have a molecular weight (determined by GPC, calibration with polystyrene sulphonates) of 1000 Da to 300 kDa, alternatively from 1000 Da to 80 kDa and in particular from 1000 Da to 15 kDa. The crystallization inhibitors are usually soluble in water, for example, at least 1 g / l, alternatively at least 10 g / l, and in particular at least 100 g / l at 20 ° C.

Solid carriers or fillers can be mineral earths, for example silicates, silica gels, talc, kaolin, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium, polysaccharide powders, for example cellulose, starch, products of plant origin, for example cereal flour, tree bark flour, wood flour, walnut shell flour and mixtures thereof.

Examples of emulsifiers that can be used are calcium salts of alkylarylsulfonic acid, such as calcium dodecylbenzenesulfonate, or non-ionic emulsifiers such as polyglycol esters of fatty acids, alkylaryl polyglycol ethers, polyglycol ethers of fatty alcohols, ethylene oxide propylene oxide condensates. , alkyl polyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.

Surfactants are surface active compounds such as anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, humectants, penetration enhancers, or protective colloid. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. Or North American Ed.).

Anionic surfactants include alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalene sulfonates, dodecyl- and naphthalene sulfonates and tridelenocylbenzenesulfonates , sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are carboxylated alkyl carboxylates and alcohol or alkylphenol ethoxylates.

Nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide, can be used for the alkoxylation. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitan, sucrose esters, and glucose. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vinyl alcohols, or vinyl acetate.

Cationic surfactants include quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or long chain primary amine salts. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or comb polymers of polyacid. Examples of polybases are polyvinylamines or polyethyleneamines.

Thickeners include polysaccharides (eg, gumxanthan, carboxymethylcellulose), organic clays (organically modified or unmodified), polycarboxylates, and silicates.

Bactericides include derivatives of bronopol and isothiazolinone such as alkyl isothiazolinones and benzisothiazolinones.

Antifreeze agents include ethylene glycol, propylene glycol, and glycerin.

Antifoaming agents include silicones, long chain alcohols, and fatty acid salts. Preferred antifoaming agents are silicones, such as polydimethylsiloxane.

Colorants (eg red, blue or green) include low water solubility pigments and water soluble dyes. Examples are inorganic dyes (eg, iron oxide, titanium oxide, iron hexacyanoferrate) and organic dyes (eg, alizarin, azo, and phthalocyanine dyes).

Tackifiers or binders include polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Anti-drift agents are, for example, nonionic polymers such as polyacrylamides, polyethylene glycols or guar gum with a molecular weight of at least 20 kDa, preferably at least 50 kDa, and in particular at least 100 kDa. Other examples of anti-drift agents are lecithin and self-emulsifying polyesters.

Humectants are typically compounds that attract and / or hold water within the adjuvant composition. Examples include glycerol or sugar syrups.

As described above, the adjuvant composition enhances the bioactivity of a pesticide, therefore, the adjuvant composition is a composition in which, when combined with a pesticide or a mixture of pesticides and applied to a target substrate, it achieves by at least 60%, 65%, 70%, 75%, 80%, or even at least 85%, or even at least 90% control. "% control", as used herein, refers to any observable measure of control of the growth of the target substrate, which may include one or more of the actions of (1) killing, (2) inhibiting growth, reproduction or growth; and (3) eliminate, destroy, or otherwise decrease the occurrence and activity of pests. Control can be measured by any of several methods known in the art.

In some embodiments, at least 80% control is achieved no more than 5, 10, 15, 20, 25, or 30 days after application of the adjuvant and pesticide compositions or pesticide mixture to the target substrate. Formulation of the adjuvant composition

In making the adjuvant compositions of the present disclosure, the individual components disclosed above are provided and combined together by standard methods, for example, by dissolving the individual components in any suitable flask or container, preferably at room temperature. The relative levels of the components are selected to give the required performance with a view to ensuring, on the one hand, that a component is present at a sufficient level to be effective but, on the other hand, that excessive cost is avoided by limiting the upper range. of the component. The order of mixing the components is not particularly important and, in general, individual components can be added sequentially or all at once.

Thus, in one embodiment, the maleated natural oil derivative and optional auxiliary components are combined together to form an adjuvant composition. According to some embodiments, the adjuvant composition includes at least about 10% by weight, and furthermore at least about 50% by weight, and still more at least about 75% by weight, and even further so less about 90.5% by weight, and even more, at least about 99% by weight of the maleated natural oil derivative where the% by weight is based on the total weight of the adjuvant composition. In another embodiment, the adjuvant composition includes less than about 90% by weight, and furthermore less than about 75% by weight, and still more less than about 45% by weight and still more less than about 29.5%. by weight of the maleate natural oil derivative, where the% by weight is based on the total weight of the adjuvant composition.

In yet another embodiment, the adjuvant composition includes (i) about 0.1-99.9% by weight of the maleated natural oil derivative and (ii) about 0.1-99.9% by weight of an auxiliary component. , where% by weight is based on the total weight of the adjuvant composition. In another embodiment, the adjuvant composition includes (i) about 0.1-50% by weight of the maleated natural oil derivative and (ii) about 0.1-50% by weight of the auxiliary component, where the% by weight it is based on the total weight of the adjuvant mixture. In yet another embodiment, the adjuvant composition includes (i) about 0.1-29.9% by weight of the maleated natural oil derivative and (ii) about 70.1-99.9% by weight of an auxiliary component. , where% by weight is based on the total weight of the adjuvant composition.

Agrochemical formulation

Another object of the present disclosure is directed to an agrochemical formulation comprising a pesticide and the adjuvant composition of the present disclosure (and auxiliary components in embodiments where said auxiliary components are not included in the formulation of the adjuvant composition.). The agrochemical formulation can be used in the treatment of target substrates as disclosed above and refers to all forms of compositions, including concentrates and spray formulations. "Spray formulations" are aqueous agrochemical formulations that include all the components that it is desired to apply to the target substrate or its environment in a form and at a concentration (dilution) appropriate for spraying. Spray formulations can be prepared by a simple dilution of concentrates containing the desired components (other than water), or by mixing the individual components, or a combination of diluting a concentrate and adding additional individual components or component mixtures. Typically such end use mixing is carried out in the spray tank from which the formulation is sprayed or in a holding tank to fill the spray tank and commonly such mixes and mixtures are referred to as tank mixing and tank mixes. . "Concentrates" are agrochemical formulations, which can be aqueous or non-aqueous, and which are designed to be diluted with water (or a water-based liquid) to form corresponding spray formulations and include such compositions in liquid form as solutions. , emulsions. or dispersions and in solid form, especially in water-dispersible solid form, such as granules or powders. "Emulsifiable concentrates" are liquid "concentrates" that include the pesticide and adjuvant composition in solution or dispersion, usually also including an emulsifier and / or surfactant, that are readily emulsified in dilution in water, typically with no more than gentle agitation.

Agrochemical formulations according to the present disclosure can be prepared by standard processes, for example, by mixing by grinding, dissolving or dispersing the individual components, preferably at room temperature. If other auxiliary components of the formulation are present, they are preferably likewise incorporated at room temperature. In general, the sequence in which the individual components are added is not of decisive importance. Thus, in one embodiment, the adjuvant composition disclosed above can be formulated in a container, eg, a stainless steel, steel, tin, aluminum can, plastic or glass bottle, and paper or cardboard container. The adjuvant composition can then be combined with a pesticide and water and / or other solvent and in some embodiments an auxiliary component to form an agrochemical formulation in the field just prior to application.

The currently described adjuvant composition is not limited for use with any particular class of pesticides. An agrochemical formulation of the presently described technology may comprise a pesticide or a mixture of pesticides.

In one embodiment, the pesticide includes any chemical or biological agent (ie, "active ingredient") used to prevent, destroy, repel, or mitigate a pest. Therefore, in a particular embodiment, the pesticide is a fungicide, herbicide, insecticide, algaecide, molluscicide, miticide, rodenticide, growth regulator or insect repellent.

According to one embodiment, the pesticide is a fungicide. Examples of fungicides include, but are not limited to: azoxystrobin, trifloxystrobin, kresoxim methyl, famoxadone, metominostrobin and picoxystrobin, carbendazim, thiabendazole, dimetomorph, vinclozoline, iprodione, dithiocarbamate, imazalil, fluconazole, prochloconazole, bluconazole, bluconazole, bluconazole. , bromuconazole, cyproconazole, difenoconazole, hexaconazole, paclobutrazol, propiconazole, tebuconazole, triadimefon, trtiticonazole, fenpropimorph, tridemorpho, phenpropidine, mancozeb, methiram, chlorothalonil, thiram, ziram, captaphol, fluatane, bicarbuatanil, zutoxin, foltapetil, fluatanil , ethyrimol, dimoxystrobin, fluoxastrobin, orisatrobin, metominostrobin, prothioconazole, 8- (2,6-diethyl-4-methylphenyl) tetrahydropyrazolo [1,2-d] [1,4,5] oxadiazepine-7,9-dione, ester of 2,2, -dimethyl-propionic acid-8- (2,6-diethyl-4-methyl-phenyl) -9-oxo-1,2,4,5-tetrahydro-9H-pyrazolo- [1,2 d ] [1,4,5] oxadiazepine-7-yl and metalaxyl.

In another embodiment, the pesticide is a herbicide. Examples of herbicides include, but are not limited to: fluzifop, mesotrione, fomesafen, tralkoxydim, napropamide, amitraz, propanil, cyprodanyl, pyrimethanil, dichlororan, technazene, toclofos methyl, flamprop M, 2,4-D, MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl, diclofop methyl, haloxyfop, quizalofop-P, indole-3-ylacetic acid, 1-naphthylacetic acid, isoxaben, tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba, diclobenyl, benfuresate, triambazole, triazole, benzene azolin teflubenzuron, phenmedipham, acetochlor, alachlor, metolachlor, pretylachlor, tenylchlor, alloxydim, butroxydim, clethodim, cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb, biphenox, oxyfluorphinyl, acifluorphene-fluorobenzethyl, acifluorofenyl, acifluorofenthyl, acifluorofenyl, imazaquin, imazetapyr, imazapic, imazamox, flumioxazin, flumiclorac-pentyl, picloram, amodosulfuron, chlorsulfuron, nicosulfuron, rimsulfuron, triasulfuron, trialate, pebulate, prosulfocarb, molinate, cia simazine, atrazine Nazine, Ametrine, Promethrin, Terbutylazine, Terbutryn, Sulcotrione, Isoproturon, Linuron, Fenuron, Chlorotoluron, Methoxuron, N-phosphonomethylglycine and its salts (glyphosate), Glufosinate, Chloromequat chloride, Paraquat and Triflo-sapheuron, Fomotrione and Phenuron sulphuron, Mesothrione and Phenuron sulphuron.

In yet another embodiment, the pesticide is an insecticide. Examples of insecticides include, but are not limited to: abamectin, acetate, acetamiprid, acrinathrin, alanicarb, aldicarb, allethrin, alpha-cypermethrin, amitraz, asulam, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, bendensfultapbcarb , beta-cyfluthrin, betacypermethrin, bifenthrin, bioalethrin, bioresmethrin, bistrifluron, borax, buprofezine, butoxycarboxime, cadusafos, carbaryl, carbofuran, chlorpropham, clothianidin, cyflutrin, cyhalilothrin, phenytoxynobrine, cyhalonthrin, phenytoxynobrine, cyhalonthrine, phenytoxycarboxymethrin, cyhalhalzulphrin , fenthion, fenvalerate, fipronil, halfenproramex, heptachlor, hydramethylnon, imidacloprid, imiprothrine, isoprocarb, lambda cyhalothrin, methamidophos, methiocarb, methomyl, nitenpyram, omethoate, permethrin, pyrimicarb, pyrimiphoxur, tebumebenocarb, pyrimiphoxyl methyl, trioxybondyloxycarb .

In a further embodiment, the pesticide is an algaecide. Examples of algaecides include, but are not limited to: betoxazine, copper dioctanoate, copper sulfate, cybutrin, diclone, dichlorophene, endothal, phenthin, hydrated lime, nabam, quinoclamine, quinonamide, simazine, triphenyltin acetate, and triphenyltin hydroxide. .

In another embodiment, the pesticide is a molluscicide. Examples of molluscicides include, but are not limited to: metaldehyde, methiocarb, and aluminum sulfate.

In yet another embodiment, the pesticide is an miticide. Examples of miticides include, but are not limited to: antibiotic miticides, carbamate miticides, formamidine miticides, mite growth regulators, organochlorine miticides, permethrin, and organophosphates.

In yet another embodiment, the pesticide is a rodenticide. Examples of rodenticides include, but are not limited to: 2-isovalerindan-1,3-dione, 4- (quinoxalin-2-ylamino) benzenesulfonamide, alpha-chlorohydrin, aluminum phosphines, anta, arsenic oxide, barium carbonate, bistiosemi, brodifacoum, bromadiolone, bromethalin, calcium cyanide, chloralose, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, diphenacoum, diphthyalone, diphacinone, ergocalciferol, flopupumaphene, chlorophacinoneCH, flammachloro-HCl hydrogen cyanide, iodomethane, lindane, magnesium phosphide, methyl bromide, norbormide, fosacetyim, phosphine, phosphorus, pindone, potassium arsenite, pyrinuron, scylliroside, sodium arsenite, sodium cyanide, sodium fluoroacetate, strychnine, sulfate of thallium, warfarin, and zinc phosphide.

In another embodiment, the pesticide is a growth regulator. Examples include, but are not limited to, abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butraline, chloromequat (chloroquat chloride), choline chloride, cyclanilide, daminozide, dicegulac, dimethypine, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepicuat (mepicuat chloride), naphthaleneacetic acid, N-6-benhexyladenine-calcium, paclobutyladenine ), prohydrojasmon, thidiazuron, triapentenol, tributyl phosphorothrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl and uniconazole.

In a further embodiment, the pesticide is an insect repellent. Examples of insect repellants include, but are not limited to: 2-ethyl-1,3-hexanediol; N-octyl bicycloheptene dicarboximide; N, N-diethyl-M-toluamide; 2,3: 4,5-Bis (2-butylene) tetrahydro-2-furaldehyde; di-n-propyl isocinchomeronate; and 2-hydroxyethyln-octyl sulfide.

The amount of pesticide included in the agrochemical formulation of the present disclosure will vary according to a series of parameters such as the target substrate to be treated, the area to be treated, etc. In general, an application rate of about five grams to about four kilograms per hectare (g / ha) of pesticide may be suitable. The amount of the adjuvant composition in the agrochemical formulation can be about 0.01-99% by weight, based on the total weight of the agrochemical formulation.

The agrochemical formulations of the present disclosure can be used in conventional agricultural methods. For example, the pesticide or pesticide mixture and adjuvant composition can be mixed with water and / or other solvents and / or fertilizers and applied post-emergence to a desired target substrate by any means, such as aircraft spray tanks, spray tanks. knapsack spraying, cattle dipping tanks, agricultural equipment used in soil spraying (eg, boom sprayers, hand sprayers), and the like.

As discussed above, according to some embodiments, the agrochemical formulation can be a concentrated composition, which can be diluted in a suitable volume of water to form a spray formulation (e.g., a tank mix composition) for application to the target substrate. The concentrate composition can be in liquid, solid or semi-solid form. In at least one embodiment, it is an aqueous concentrate composition.

For example, in one embodiment, the amount of pesticide in the concentrate composition can be about 1% by weight to about 80% by weight, alternatively from about 16% by weight to about 60% by weight, alternatively from 35% by weight to about 55% by weight, based on the total weight of the composition of concentrate. The amount of the adjuvant composition in the concentrate composition may be from about 0.0001% by weight to about 20% by weight, alternatively between about 0.001% by weight and about 15% by weight, or alternatively from about 0.01% by weight to about 10% by weight, or alternatively from about 0.1% by weight to about 5% by weight, or even alternatively from about 0.5% by weight to about 3 % by weight, based on the total weight of the concentrate composition.

The concentrate composition can be diluted by a user with water to produce a spray formulation containing from about 0.01% by weight to about 15% by weight, alternatively from about 0.1% by weight to about 5%. % by weight, alternatively from about 0.2% by weight to about 2% by weight of the pesticide, based on the total weight of the spray formulation. The spray formulation may typically contain from about 0.0001% by weight to about 3% by weight, alternatively from about 0.001% by weight to about 1% by weight, alternatively from about 0.01% by weight to about 0.5% weight percent of the adjuvant composition of the present disclosure.

In some other embodiments of the present disclosure, the pesticide and adjuvant composition are combined to form a "ready-to-use" (RTU) spray formulation. The RTU spray formulation can be prepared by a user by diluting a concentrate composition as described above, or alternatively it can be provided to the user as is. For example, the TUR spray formulation may contain from about 0.5% by weight to about 5% by weight, alternatively from about 0.75% by weight to about 3% by weight, alternatively from about 1% 5% by weight to about 2.5% by weight of the pesticide, based on the total weight of the RTU spray formulation. The TUR spray formulation may contain from about 0.01% by weight to about 2.5% by weight, alternatively from about 0.2% by weight to about 2% by weight, alternatively from about 0 5% by weight to about 1% by weight of the adjuvant composition of the present disclosure. The remainder of the TUR composition can be water.

According to another embodiment, the presently described technology provides a method of killing or inhibiting or repelling a pest comprising the steps of providing a pesticide or a mixture of pesticides in a pesticidally effective amount; to provide an effective amount of an adjuvant composition of the present disclosure, combine the pesticide or pesticide mixture with the adjuvant composition to prepare an agrochemical formulation, and contact the agrochemical formulation and the pest.

Examples

Example 1: Maleated natural oils

In a representative experiment, 1029 g of soybean oil was heated to 80 ° C and 183 g of molten maleic anhydride (15% w / w of the total reaction) was added, along with 6 g of toluene. The mixture was heated at 200 ° C for 5 hours in a round bottom flask equipped with a stir bar and a reflux condenser, and then toluene was removed under reduced pressure to produce maleated soybean oil (MASBO-15). Similar experiments were carried out to produce MASBO-5, MASBO-10, MASBO-20 and MASBO-25, where the number corresponds to the weight percentage of maleic anhydride that was reacted on the soybean oil. Other derivatives were synthesized in a similar way using different oils where the oil was either linseed oil (MALSO-N °) or glycerol trioleate, a synthetic triglyceride made from glycerol and oleic acid (MAGTO-N °).

Example 2: Maleate Amine Modified Oils

In a representative experiment, MASBO-15 (407.5 g) was added to a round bottom flask and heated to 40 ° C. Then, 623.0 g of JEFF AMINE® M-1000 polyetheramine was added while stirring. This mixture was stirred for 2 hours at 40 ° C and then 257.4 g of 2-butoxyethanol was added as a solvent to give MASBO-15A. When diluted in water, MASBO-15A formed a microemulsion. Other amines were reacted in a similar manner to produce the products listed in Table 1 below.

Example 3: Maleated oils modified with mPEG (not according to the invention)

In a representative experiment, MASBO-20 (50.0 g) was added to a round bottom flask and heated to 50 ° C. Then, 66.0 g of mPEG-650, a 650 MW monomethyl polyethylene glycol, and the reaction was stirred and heated at 80 ° C for 2 hours. Upon cooling, the product was a waxy solid that slowly dispersed to form a microemulsion in water (MASBO-20A). Other mPEGs were reacted in a similar manner to produce the products listed in Table 1 below.

Below is a summary of the compounds that were prepared and how they performed when diluted with 342 ppm WHO water.

Field tests

Field trials are necessary to test the ability of the new adjuvants to increase the efficacy of pesticides. The MASBO-10N sample was used in a field trial to test its adjuvant ability with two different herbicide systems (glyphosate, supplied as Touchdown HiTech® from Syngenta Corporation, and dicamba, supplied as Clarity® from BASF Corporation) against others. common adjuvants known to those of skill in the art. The results are shown below in Table 2.

As shown in Table 2, MASBO-10N was able to increase the efficacy of the herbicidal system (versus control) and compared favorably with many standard adjuvants. This indicates that the maleated natural oil derivatives of the present disclosure have great utility as adjuvant compositions for use with pesticides. Due to their relative ease of manufacture and formulation, they can be more advantageous than adjuvants of similar performance.

Table 3 contains the results of another field trial using glyphosate and saflufenacil, a common herbicide combination (glyphosate supplied as Touchdown HiTech® from Syngenta Corporation and saflufenacil supplied as Laudis® from Bayer CropScience).

continuation

In Table 3, the MASBO derivative again improves the efficacy of herbicides and compares favorably with other well-known adjuvant classes. This indicates that the maleated natural oil derivatives of the present disclosure have great utility as adjuvant compositions for use with pesticides. Due to their relative ease of manufacture and formulation, they can be more advantageous than adjuvants of similar performance.

Table 4 shows the comparison of a different variation of the MASBO adjuvant, MASBO-15B with glyphosate and saflufenacil, the same herbicides used in Table 3. In this example there is no cosurfactant formulated with MASBO, and the performance still compares favorably, working as well or better than many well known adjuvants. This indicates that the maleated natural oil derivatives of the present disclosure have great utility as adjuvant compositions for use with pesticides. Due to their relative ease of manufacture and formulation, they can be more advantageous than adjuvants of similar performance.

Claims (11)

1. An adjuvant composition comprising a maleate compound obtained from the reaction of (1) a maleate oil derived from renewable raw material resources that have been reacted in an ene reaction with an α, p-unsaturated carboxylic acid or anhydride that introduced fractions additional carboxylic compounds or the related anhydrous structure in the oil molecules with (2) a compound comprising at least one polyetheramine, wherein the molar ratio of the maleate oil (1) with the compound (2) is greater than 1.1: 1. 2. The adjuvant composition according to claim 1, wherein the maleate oil is a maleate vegetable oil. The adjuvant composition according to claim 2, wherein the maleated vegetable oil is a maleate soybean oil. 4. The adjuvant composition according to claim 1, wherein the maleate oil is a maleate alkyl ester of a fatty acid. 5. The adjuvant composition according to claim 1, wherein the polyetheramine is a polyether monoamine. The adjuvant composition according to claim 1, wherein the adjuvant composition further comprises one or more auxiliary components. 7. An agrochemical formulation comprising a pesticide or mixture of pesticides and the adjuvant composition according to claim 1. 8. The agrochemical formulation according to claim 7, wherein the pesticide is a fungicide, herbicide, insecticide, algaecide, molluscicide, miticide, rodenticide or insect repellent. 9. A concentrate composition comprising from about 1% by weight to about 80% by weight of a pesticide and from about 0.0001% by weight to about 20% by weight of the adjuvant composition of claim 1 , wherein the% by weight is based on the total weight of the concentrate composition. 10. A spray formulation comprising a pesticide, the adjuvant composition according to claim 1 and water or another solvent. 11. A method of killing or inhibiting or repelling a pest comprising the steps of providing a pesticide or a mixture of pesticides in a pesticidally effective amount; providing an effective amount of an adjuvant composition according to claim 1, combining the pesticide or pesticide mixture with the adjuvant composition to prepare an agrochemical formulation, and contacting the pesticide formulation and the pest.